KR20160011191A - Process for the preparation of a metal-organic compound - Google Patents

Abstract

Providing a first reactant comprising at least one metal in ionic form; Providing a second reactant comprising at least one organic ligand capable of associating with the metal in ionic form; And mixing the first and second reactants under long-term, sustained pressure and shear conditions long enough to synthesize the metal-organic compound, wherein the metal- A method is provided herein wherein an organic compound comprises at least one metal ion and at least one organic ligand, and wherein the organic ligand can be associated with the metal ion.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for preparing a metal-organic compound,

The present invention relates to a process for the preparation of metal-organic compounds, to compounds obtained in this way and to their use.

The metal-organic compound is a compound comprising at least one metal ion and at least one organic group chemically bonded to the metal ion. These are variously referred to as organometallic compounds, coordination compounds, coordination complexes and metal complexes. The organic group bound to the metal is often referred to as a " ligand ". Typically, an organic group is bonded to a metal ion through a carbon, nitrogen, oxygen, silicon, phosphorus or sulfur atom, but they can also bind through an arsenic or selenium atom. The descriptive term " organometallic " generally has a subset of such compounds in which an organic group is bonded to a metal ion through a carbon atom.

Metal organic compounds have been described in standard chemistry textbooks such as inorganic chemistry [Housecroft and Sharpe, Pearson Education Limited, Edinburgh, first edition 2001], inorganic chemistry [hriver and Atkins, Oxford University Press, Oxford, fourth edition, 2006] Chemistry II, ed. J. A. McCleverty and T.J. Meyer, Elsevier, 2004 and Comprehensive Organometallic Chemistry II, ed. E. W. Abel, F. G. A. Stone and G. Wilkinson, Elsevier, 1995.

All metal ions can form metal-organic complexes. Specific examples include ^{Li +, Na +, K +} , Mg 2 +, Ca 2 +, Sr +, Ba 2 +, Sc 3 +, Y 3+, Ti 4 +, Zr 4 +, Hf 4 +, V 4+ , V ^3+, V ^2+, Nb ^{+ 3,} Ta ^{+ 3,} Cr ^3+, Cr ^{4 +,} Cr ^{+ 6,} Mo ^{+ 3,} Mo ^{+ 6,} W ³⁺ Mn ^{3 +,} Mn ^{+ 2,} Re ^{3 +,} Re ^{+ 2,} Fe ^{+ 3,} Fe ^{+ 2,} Ru ^{+ 3,} Ru ^{+ 2,} Os ^{+ 3,} Os ^2+, Co ^{+ 3,} Co ^{+ 2,} Rh ^{+ 2,} Rh ^+, Ir ^{+ 2,} Ir ^{+, Ni 2 +, Ni +} , Pd 2 +, Pd +, Pd 4 +, Pt 2 +, Pt +, Pt 4 +, Cu 2+, Cu +, Ag +, Au +, Au 3 +, Zn 2 ^+, Cd ^{+ 2,} Hg ^{+ 2,} Al ^{+ 3,} Ga ^{+ 3,} In ^{+ 3,} Ti ^{+ 3,} Si ^{+ 4,} Si ^{2 +,} Ge ^{+ 4,} Ge ^2+, Sn ^{+ 4,} Sn ^{+ 2,} Pb ^{4 +,} Pb ^{2 +,} as ^{5 +,} as ^{3 +,} as ^+, Sb ^{5 +,} Sb ^{3 +,} Sb ^+, Bi ^{5 +,} Bi ^{3 +} and Bi ^+, as well as the lanthanide ion, for example, ^{3 +} La, Ce ^{3 +,} Ce ^{4 +,} Pr ^{+ 3,} Nd ^{+ 3,} Pm ^{+ 3,} Sm ^3+, Eu ^{+ 3,} Gd ^{+ 3,} Tb ^{+ 3,} Dy ^{+ 3,} Ho ^{+ 3,} Er ^{3 +,} Tm ^{+ 3,} Yb ^{+ 3,} Lu ^{+ 3} and actinide element ions, for example, ^{3 +} Th, Pa ^{+ 3,} U ^3+, U ^{6+, 3 +} Np, Pu ^{3 +, 3 +} Am, Cm ^{3 +} , Bk ^{3 +} , Cf ^{3 +} , Es ^{3 +} , Fm ^{3 +} , Md ^{3 +} , No ^{3 +,} and Lr ^{3 +} .

The methods used to synthesize such compounds generally include the use of suitable solvents to dissolve or partially dissolve either or both of the reactants that provide the organic groups and the metal-containing reactants. Solvents are generally present in very large excess. The use of such solvent-based methods increases the technical complexity, time and cost of synthesis. Environmental contamination can also be present from such a large amount of such solvents as in industrial processes. Many organic solvents are poisonous to the environment and / or harmful. Therefore, it is highly desirable to synthesize a metal organic compound in the absence of a solvent. The solventless method of synthesis has been relatively undeveloped, but includes milling with a solid reactant, for example, using a mortar and a pestle or a ball mill [A. Garay, A. Pichon and S.L. James Chem. Soc. Rev., 2007, 36, 846]. Alternatively, solventless synthesis may be achieved by causing one or both of the reactants to be in the gaseous phase [P. L. Timms, Chem. Soc. Rev., 1996, 93; A. S. Filatov, A. Y. Rogachev and M. A. Petrukhina, Cryst. Growth Des., 2006, 6, 1479]. Alternatively, one reactant or both reactants can be induced to melt [M. Bala, N.J. Coville J. Organomet. Chem. 2007, 692, 709]. However, there is a continuing need for a solvent-free process that can work on a continuous basis rather than in a batch-wise manner, and that can be easily scaled up for the synthesis of larger amounts of product.

The subset of metal organic compounds is referred to as the " metal-organic framework " (MOF).

The metal-organic structure is a crystalline or non-crystalline porous metal-organic compound having a specific pore or pore distribution and a large specific surface area. In recent years, these have become the object of comprehensive research work in particular. Applications include catalysis or separation, storage, and release of various compounds and gases.

Metal-organic structures are well known in the art and are provided in the literature under various names including coordination polymers, metal-organic coordination networks (MOCN) and porous coordination polymers (PCP) .

In MOF, the organic groups are bridged between the metal ions to form a polymer structure. Such a polymer network can be extended to one-dimensional, two-dimensional or three-dimensional. Of particular interest are those that expand to two or three dimensions, since such a structure may be porous. In particular, they may contain voids capable of accepting other molecules. When other molecules are absorbed into the pores, the metal-organic structure can be described as a host, and absorbed molecules can be described as a guest. The absorption of the guest into the cavity can be caused by a simple exposure of the MOF to the guest in the event that the guest is in liquid or gaseous form so that they can be dispersed into the porous structure. Because pores have a certain size, shape, and chemical functionality, such materials can exhibit selectivity for the absorption of a particular guest. Thus, the nature of the porosity results in possible applications such as applications requiring storage, separation or release of guest species. For example, a liquid or gas can be stored in such a material, a mixture of gases can be separated into its components using such a material, a mixture of liquids can be separated into its components using such a material, Guest may be released by such material. Such materials can also act as sensors for the guest, either as catalysts by facilitating chemical changes in the guest, or through guest-induced changes in one or more of the physical properties of the MOF.

General information on various known MOFs and conventional synthetic methods is found, for example, in "Metal-organic frameworks," James, S. L., Chemical Society Reviews 32 (2003) 276-288; "Metal-Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials," Meek, S. T. et al., Advanced Materials 23 (2011) 249-267; Long, J. (ed.) Chemical Society Reviews, Metal Organic Frameworks theme issue, 2009, vol. 38]. The preparation of Cu-BTC MOF (also known as HKUST-1) is described in Chui et al., Science 283 (1999), 1148-1150, wherein a copper salt, i.e., copper nitrate trihydrate, , The salt and trimesic acid (H3BTC) are dissolved in a solvent mixture of water and ethanol to synthesize a MOF material. Here, the ratio of the mass of the solvent to the mass of the reactant was 1664%.

For example, the preparation of MOF ZIF-8 is described in Park et al., Proceedings of the National Academy of Science 27 (2006) 10186-10191, wherein a zinc salt (zinc nitrate) The salt and 2-methylimidazole (H-MeIM) are dissolved in solvent N, N'-dimethylformamide (DMF) to synthesize MOF. Here, the ratio of the mass of the solvent to the mass of the reactant was 6320%.

For example, Chen et al., Science 291 (2001), 1021-1023 describe the preparation of MOF-14, wherein a copper salt (copper nitrate) is used as the starting material, , 4 "-benzene-1,3,5-triyltribenzoic acid (H3BTC) is dissolved in a solvent mixture of N, N'-dimethylformamide (DMF), ethanol and water to synthesize MOF, Was 2444%. ≪ tb > < TABLE >

As described in that reference, many methods have been developed to synthesize MOF using precursors including metal precursors and corresponding organic ligands. However, most require the use of more than one solvent and heat. The yields obtained using these methods are suitable for laboratory use, but they require time, the separation of additional materials (e.g., solvents), and the use of solvents that are inefficient on an industrial scale in terms of heating and which are not further environmentally friendly .

Synthesis can be described as a process of forming chemical bonds that together secure the structure structure of a material. After synthesis, microporous materials, such as metal organic structures, typically contain molecules, e. G., Solvent molecules, or by-products of synthesis, in their pores. Thus, such materials typically require processes known to work to remove these species so that voids become vacant and available for sorbates of interest. The work typically consists of heating, depressurizing or washing with another solvent, or any combination of such procedures. Such methods are well known in the art and do not form part of the actual synthesis of the material. Thus, these processes may also require activation of the material as produced by the methods described in this patent.

Reduced solvent or solvent-free synthesis of such metal-organic metallic structures is desired. WO 2007 / 023295A2, the entirety of which is incorporated herein by reference, describes processes for the preparation of metal-organic structures by milling, such as in a ball mill, completely or substantially in the absence of solvent. However, continuous production processes are needed to increase the yield of products that can be produced by industrial production.

In the following discussion, the term "metal organic compound" includes a porous crystalline metal-organic structure as a subset.

Recently, the potential of extrusion in pharmaceutical synthetic applications has begun to be known. US 2011 / 0177126A describes a method for producing a co-crystal by exposing a mixture of two co-crystal precursors to a long, continuous condition of pressure and shear, preferably in an extrusion process. However, such a decision is fixed together only by non-sharing forces, i. E., Low binding energy.

One object of the present invention is to provide a continuous process for the production of metal-organic compounds which can provide economical yields with increased efficiency in terms of material, time, cost or energy, as well as environmentally friendly and solvent-based processes .

Accordingly, the present invention provides a method of producing a metal-organic compound, comprising: providing a first reactant comprising at least one metal in ionic form, and a second reactant comprising at least one or more organic ligands; Mixing the first and second reactants together; And exposing the mixture of the first and second reactants to long and continuous conditions of pressure and shear sufficient to form the metal-organic compound.

Surprisingly, we have found that the metal-organic compounds described as requiring solvent-based formation only in the prior art now only mix the selected metal ion (s) and the organic ligand (s) together and form a covalent bond Lt; RTI ID = 0.0 > pressure and shear conditions. ≪ / RTI > In this way, the metal-organic compound can be formed without using a conventional solvent thermal process. Unlike prior art processes, there is no apparent liquid phase that is observed at any time during the process of the present invention.

This can be accomplished completely in the absence of solvent, preferably by giving the components to an extrusion process.

Extensive industrial use of extruders is commonplace in the plastics, rubber and food industries. Most conventional polymer processing machines can be configured for use in Good Manufacturing Practices (GMP) environments. Extrusion processing operations can be easily scaled from laboratory to manufacturing scale.

The process of the present invention is also suitable for use with the same combination of metal and organic ligands in ionic form for use in conventional solvent-based processes known in the art, for example, as discussed above.

Surprisingly, the present inventors have found that the achievable change according to the invention is possible with a very short residence time from as short as a few seconds up to 40 minutes. The first and second reactants are exposed to continuous conditions of pressure and shear for at least 1 minute, preferably 2 minutes or more, especially 2 to 40 minutes, especially 2 to 30 minutes. It will be appreciated that the time required to form the metal organic compound will generally depend on the degree of pressure and shear conditions the first and second materials are exposed to, but long and continuous exposure typically results in improved metal-organic compound formation It turned out. In many cases, however, there will be a balance between the possible decomposition of the organic ligand over the long time spent under shear and pressure conditions and the time required for metal-organic compound formation. In addition, excessive exposure to high shear and / or high temperatures for the formation of metal-organic structures may reduce or eliminate the crystallinity of the material. Such balance will depend on the material used and the conditions applied to such material, which can be determined by one skilled in the art.

In a preferred embodiment, the pressure and shear are applied in an extrusion process. It is surprising that the extrusion process can be used to obtain metal organic compounds including crystalline and amorphous porous metal-organic structures. Extrusion also provides a method for producing metal-organic compounds in high yields and in large quantities. This provides a considerable advantage over conventional metal-organic compound synthesis techniques. Surprisingly, extrusion causes quantitative and very precise chemical transformations, including destruction or formation of strong chemical bonds, such as chemical bonds between Al and O (typically about 450 kJ / mol), while preserving high crystallinity in the resulting product (I.e., providing a single crystalline phase). That is, the pressure and shear conditions applied to the reactants can be expected to destroy the material in a long-range order to make it amorphous. Surprisingly, the present inventors have found that this is not the case.

Extrusion means conveying material through a long lumen as pressure and shear are applied; Typically, pressure and shear are applied at least in part by means of conveying material through the lumen. Extrusion may also include passing the material through the die to make any shape or otherwise adjust the product of the extrusion process, but this is generally not necessary for metal-organic compound formation.

Generally, extrusion is preferably a screw-based extrusion process. While uniaxial extrusion may be suitable for some embodiments, it is generally preferred that the method is a screw-based extrusion method in which two or more screws interact with a mixture of the first and second reactants during the extrusion process. Such a method makes it possible to mix and mix the mixture to a greater extent to obtain the desired metal-organic compound.

In a preferred embodiment, the screw-based extrusion method is a biaxial extrusion method. The biaxial method provides a useful balance that minimizes the complexity of the extruder while providing the ability to adjust the extrusion process as desired. Of course, it is possible that an extrusion process in which three or more screws interact can be used, and such systems are well known for extrusion of polymers.

In general, when a biaxial extrusion method is used, it is preferably a co-rotating method. However, in some embodiments, it can be found that the counter-rotating method provides some advantages.

Reverse-rotation screws are used when very high shear is required because they create high pressure and shear forces between the two counter-rotating screws. Thus, a counter-rotating screw may be useful where very high levels of shear and pressure are desired to form metal-organic compounds. However, reverse rotation screw systems may have problems with air entrainment, low maximum screw speed and yield; These may be disadvantages in certain applications.

The co-rotating system can achieve a good level of mixing and transport of the material, and is also operated at a high speed, thereby achieving high production rates. They are less likely to wear than reverse-rotating systems.

In the presence of more than one screw, it is preferred that the screws are at least substantially engaged, preferably fully engaged. The pair of screws can be considered to be fully engaged when the flight tip of the spiral threaded region of each screw reaches substantially the root of the other screw; There will typically be a small gap that provides mechanical clearance, but generally this gap will be kept to a minimum. In an effort to quantify these conditions, it is preferred that the gap between the flight tip of one screw and the root of the other screw is 10% or less, more preferably 5% or less of the total width of the root of the screw, It may be proposed that the screw of the screw portion substantially engages. The engagement system has the advantage that they are self-wiping and prevent local overheating of the material within the system.

Of course, it should be noted that in certain embodiments of the invention, it may be desirable to use a non-engagement system. Non-engagement systems can be used when it is desired that large amounts of volatile material are removed from the system, or where highly viscous materials can result in unacceptably high levels of torque applied to the system.

Another possible type of extruder for use in the present process is a recycled extruder. The recycled extruder is typically a biaxial system in which materials of one batch can be processed for a predetermined period of time until released from the system. Such extruders, such as Haake Minilab, may be useful for a variety of applications, but are not widely used as more conventional non-recycled extruders.

Generally, as is known by those skilled in the art, it is preferred that the process can be carried out only with the first and second reactants capable of forming the metal organic compound.

(i) the first reactant

The first reactant may be in the form of a salt or salt such as nitrate, nitrite, sulfate, hydrogensulfate, oxide, halide, acetate, oxide, hydroxide, benzoate, alkoxide, carbonate, Carbonates, fluorides, chlorides, bromides, iodides, phosphates, hydrogenphosphates, or dihydrogenphosphates, and the like.

Suitable metal ions are ^{Mg 2 +, Ca 2 +,} Sr 2 +, Ba 2 +, Sc 3 +, Y 3+, Ti 4 +, Zr 4 +, Hf 4 +, V 4+, V 3+, V 2 ^+, Nb ^{+ 3,} Ta ^{+ 3,} Cr ^{+ 3,} Mo ^{+ 3,} W ^3+, Mn ^{+ 3,} Mn ^{+ 2, 3 +} Re, Re ^{+ 2,} Fe ^{+ 3,} Fe ^{+ 2,} Ru ^{+ 3, 2 +} Ru, Os ^3+, Os ^{+ 2,} Co ^{+ 3,} Co ^{+ 2,} Rh ^{+ 2,} Rh ^+, Ir ^{+ 2,} Ir ^+, Ni ^{2 +,} Ni ^+, Pd ^{+ 2,} Pd ^+, Pt ^{2 +, Pt +, Cu 2 +} , Cu +, Ag +, Au +, Zn 2 +, Cd 2 +, Hg 2 +, Al 3 +, Ga 3 +, In 3 +, Ti 3 +, Si 4 +, ^{2 +} Si, Ge ^{+ 4,} Ge ^{2 +,} Sn ^{4 +,} Sn ^2+, Pb ^{4 +,} Pb ^{2 +,} As ^{+ 5,} As ^{+ 3,} As ^+, Sb ^{+ 5, 3 +} Sb, S ^{b +} , Bi ^{5 +} , Bi ^{3 +} , and Bi ⁺ can be specifically mentioned. Especially preferred is ^{Cu 2 +, Cu +, Fe} 2 +, Fe 3 +, Zn 2 +, Co 3 +, Co 2 + and Mg ^{+ 2.} Especially preferred is Cu ^{2 +,} Cu ⁺ and Zn ^{+ 2.} However, other ions may also be considered by those skilled in the art.

(ii) a second reactant for the metal organic compound

The second reactant organo group may be bonded to the metal via one or more atoms. When bonded through one atom, they are referred to as monodentate. Examples of monodentate organic ligands include pyridine, imidazole, imidazolate, nitrile, tertiary amine, secondary amine, primary amine, amide, tertiary phosphine, secondary phosphine, primary phosphine, thioether, thiolate, ether, Carboxylates, alkoxides, and aryl oxides, and the like. A wide variety of functional groups can be present on such ligands and these ligands do not bind to the metal but give various properties such as desired solubility, optical properties, electronic properties and the like, . In the latter case, they may be, for example, an electron donating group or an electron withdrawing group. The substituents may also give the desired stereoscopic characteristics. The ligand may also be chiral. In addition to a monodentate ligand, a ligand can bind to the same metal through one or more atoms. In such cases, the ligand is known as a chelate. They are called bidentate chelates when bound through two atoms, and are called tridentate chelates when they bind through three atoms. Any combination of the types of linking groups may occur in the chelate ligand. Thus, an important example of a chelate includes 2,2'-bipyridine that binds through two pyridine groups, as well as 8-quinolinate bonded through one N and one O atom. Additional examples of bidentate organic ligands include diphosphines such as BINAP. Important tridentate ligands include terpyridine. Higher digits are also common, and an example of a six-membered ligand is ethylenediamine tetraacetate (EDTA). The organic ligand can also be in the form of a large ring in which the metal ion is bound to one or more atoms of the ligand. Such ligands are referred to as macrocycles and important examples are porphyrins, phthalocyanines, tetramines such as cyclam and cyclic polyethers such as crown ethers such as 15-crown-5 and 18- Crown-6. The ligand may also be in the form of a cage within which metal ions are bound to one or more atoms of the ligand. Such ligands are referred to as cryptands, which are well known in the art.

This reaction can be considered in relation to the acid-base reaction. In particular, when an organic ligand is added in the form of a carboxylic acid, it is converted to a metal salt of a carboxylic acid by providing a proton to a basic anion of the metal salt (e.g., hydroxide ion of the metal hydroxide, or oxide- It can be considered as Brønsted acid. Water is formed as a by-product in certain cases. The ligands added in sulfonic acid, imidazole, and phosphonic acid forms can be considered to act as Bronsted acids in a similar manner to carboxylic acids.

Alternatively, when the ligand is intended to bind to the metal ion through an amine or pyridine functional group that does not contain a readily lost proton, the ligand is coupled to a Lewis acid Lt; RTI ID = 0.0 > Lewis < / RTI > base adduct or complex.

In this respect, such reactions are generally understood to be thermodynamically desirable, but they are generally too slow to occur between two solid reactants which are actually useful. Thus, such a reaction is usually carried out in a solution requiring a large amount of solvent, or as shown herein, by pulverizing the solid reactants together to induce sufficient shearing and mixing of the solid reactants.

(iii) a second reactant for the metal organic structure

In the case of a metal organic structure, the second reactant comprises at least one or more than two strands of an organic bridging ligand.

The term " two-digit or more organic compound "used within the scope of the present invention means that two or more, preferably two, coordination bonds are formed in a given metal ion and / or two coordination bonds are formed in two or more, Quot; refers to an organic compound comprising at least one functional group capable of forming a bond.

Examples of the functional group to be mentioned that the coordination bond can be formed, inter alia comprises the following functional _{groups: -CO 2 H, -SO 3 H} , -Si (OH) 3, -PO 3 H,, -CN, -NH 2 , -NHR or -NR _2. Two or more such groups may be bonded to an organic group, i.e., R ', and R' is an alkylene group having, for example, preferably 1, 2, 3, 4 or 5 carbon atoms, Propylene, n-butylene, i-butylene, t-butylene or n-pentylene or an aryl group containing one or two aromatic nuclei such as a C ₆ ring , Which may be condensed or unconjugated and may be substituted independently of each other by each of one or more substituents in a suitable manner and / or may each independently contain one or more heteroatoms such as N, O and / or S have. Two or more functional groups can in principle be coupled to any suitable organic compound, so long as it is ensured that the organic compound having such functional groups can form coordination bonds and produce a structural material.

Organic compounds comprising two or more functional groups are preferably derived from compounds which are both saturated or unsaturated aliphatic or aromatic compounds or both aliphatic and aromatic.

The aliphatic moiety or aliphatic moiety of both aliphatic and aromatic compounds is linear and / or branched and / or cyclic, and multiple rings per compound are also possible. More preferably, the aliphatic moiety or the aliphatic moiety of the compound of both aliphatic and aromatic is 1 to 15, more preferably 1 to 14, still more preferably 1 to 13, still more preferably 1 to 12 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, more preferably 1 to 11, particularly preferably 1 to 10 C atoms. Especially preferred in this context are methane, adamantane, acetylene, ethylene butadiene or benzene.

The aromatic moiety of an aromatic compound or of both aliphatic and aromatic compounds may have one or more nuclei, such as 2, 3, 4 or 5 nuclei, wherein the choice of nuclei is individual and / Are present in the condensed form. Particularly preferably, the aromatic moiety of the aromatic compound or of both aliphatic and aromatic compounds has 1, 2 or 3 nuclei, with one or two nuclei being particularly preferred. Independently of each other, each nucleus of the above-mentioned compounds may additionally comprise one or more heteroatoms such as N, O, S, B, P, Si, Al, preferably N, O and / have. More preferably, the aromatic moiety of the aromatic compound or of both the aliphatic and aromatic compounds comprises one or two C ₆ nuclei and the two nuclei are in separate or condensed forms. The aromatic compounds mentioned are in particular imidazolates, benzenes, naphthalenes and / or biphenyls and / or bipyridyls and / or pyridines.

Examples mentioned within the scope of the present invention of imidazole-based ligands are imidazole, 2-methylimidazole, 2-ethylimidazole and benzimidazole.

Examples mentioned within the scope of the present invention are:

(a) dicarboxylic acid

1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,4-butanedicarboxylic acid, tartaric acid, glutaric acid, oxalic acid, Heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,3-pyridine-dicarboxylic acid, 1,3-butadiene-1 Benzene dicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methyl-quinoline-3,4-dicarboxylic acid, quinoline-2,4 Dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4-diaminephenylmethane-3,3'-dicarboxylic acid, quinoline- Dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene- 3,4-dicarboxylic acid, 2-isopropyl-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicar Perylen-3,9-dicarboxylic acid, perylenicarboxylic acid, fluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene- Carboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl- Dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis- (phenylamino) -benzene-2,5-dicarboxylic acid, 1-1 'dinaphthyl-8,8'-dicarboxylic acid , 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilino anthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-dicarboxylic acid, 1,4- Methyl-piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, l- (4-carboxy) Dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindan dicarboxylic acid, 1,3-dibenzyl- 4-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxo-imidazolidin- -Buyquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxydoundecandicarboxylic acid, 0-hydroxy-benzophenone-dicarboxylic acid, Dicarboxylic acid, pyruleol E400-dicarboxylic acid, fluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinecarboxylic acid, 5,6- 4,4'-diaminodiphenyl ether-di-imidic dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diamino-diphenyl sulfone diimide Dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid , 8-nitro-2,3-naphthoic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H) -oxo-thio Dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazocydicarboxylic acid, 4-cyclohexene- -Dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, Dicarboxylic acid, eicosanedicarboxylic acid, 4,4'-dihydroxy-diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl- Dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluoro- Carboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2'5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, Dicarboxylic acid, 3,5-dicarboxylic acid, 3,5-dicarboxylic acid, 3,5-dicarboxylic acid, 3-dicarboxylic acid, Heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecane, 5,6-dihydro- Or 5-ethyl-2,3-pyridinedicarboxylic acid;

(b) tricarboxylic acid

2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetric tricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4- 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1 -hydroxy-1,2,3-propane, 4,5-dihydro- Oxo-lH-pyrrolo [2,3-F] quinoline-2,7,9-tricarboxylic acid, 5-acetyl- 5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid or aurintricarboxylic acid;

(c) Examples of tetra-tricarboxylic acids are as follows:

1,1-dioxide-perilla [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid such as perylene 3,4,9,10-tetracarboxylic acid or phage Lyren-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid , Decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxycyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5 -Benzene tetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8- Naphthalene tetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, tetrahydropyranetetracarboxylic acid or cyclopentanetetracarboxylic acid, such as cyclo Pentane-l, 2,3,4-tetracarboxylic acid.

Most particularly preferred within the scope of the present invention are the use of at least mono-substituted mono-, di-, tri-, tetra-, or polynuclear aromatic di-, tri-, or tetracarboxylic acids, Quot; optionally " includes at least one heteroatom, wherein two or more nuclei may comprise the same or different heteroatoms. For example, it is possible to use mono-, di-, or tricarboxylic acids, monocyclic dicarboxylic acids, mononuclear tricarboxylic acids, mononuclear tetracarboxylic acids, binuclear dicarboxylic acids, dinuclear tricarboxylic acids, dinuclear tetracarboxylic acids, trinuclear dicarboxylic acids, trinuclear tricarboxylic acids, Nuclear tetracarboxylic acids are preferred. Examples of suitable heteroatoms are N, O, S, B, P, Si, Al, and preferred heteroatoms in this context are N, S and / Suitable substituents mentioned in this connection in particular are -OH, a nitro group, an amino group or an alkyl or alkoxy group.

Accordingly, the invention also relates to a process as described above, wherein the at least two-ply organic compound is an aromatic di-, tri- and / or tetracarboxylic acid.

Particularly preferred two-digit or more organic compounds used in accordance with the present invention are acetylenic dicarboxylic acid (ADC), benzene dicarboxylic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid such as 4,4'-biphenyldicarboxylic acid (BPDC) Dicarboxylic acids such as 2,2'-bipyridine dicarboxylic acids such as 2,2'-bipyridine-5,5'-dicarboxylic acid, benzenetricarboxylic acids such as 1,2,3-benzenetricarboxylic acid or 1 (BTC), adamantanetetracarboxylic acid (ATC), adamantandibenzoate (ADB), benzene tribenzoate (BTB), methane tetrabenzoate (MTB), adamantanetetra Benzoate or dihydroxyterephthalic acid, such as 2,5-dihydroxyterephthalic acid (DHBDC).

Most particularly preferred within the scope of the present invention are especially terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid or 2,2'- 5,5'-dicarboxylic acid.

Further examples of metal-organic compounds that can be made by the present invention are listed in the accompanying Table 1.

Preferably, the process is a continuous process.

The first and second reactants may be mixed prior to passing through an extruder.

The extrusion process may be a dry extrusion process.

Liquids which can or can not act as solvents, optionally one or more liquids, are generally not required, but may optionally be added. Such liquids can be any in-situ, i.e., any material, including organic solvents and water that are liquids, form liquids, or otherwise become liquids during the process of the present invention. Such a liquid can act as a lubricant more than a solvent, but continues to have some solvating power. Thus, the process of the present invention is carried out completely or substantially in the absence of solvent, since any liquid added can also be unintentionally and even daily. (For example, <500% wt, <400% wt, <200% wt, 100%, 75% or even <50%, or even <20% or <10% % Or also < 5%) can thus still be included as an additive to assist the process progressing due to the grinding action. In one embodiment, < 500% wt is used.

It is also noted that the one or more byproducts of the process of the present invention may be solvents or solvents, such as water or an organic acid such as acetic acid. Such by-products are not intended to be part of the process of the present invention.

The mixture of first and second materials may be preferably exposed to further heat. By "additional heat" it is meant that the mixture has heat applied outside of ambient temperature and in addition to heat generated by friction during the extrusion process.

In certain embodiments, the process is preferably performed at a temperature that can cause partial melting of the reactants and / or products during at least a portion of the duration of the process. Increased fluidity resulting from such partial or complete melting may result in increased reactivity in some cases, for example, to cause the reaction to occur or allow the reaction to occur in a shorter time. In such a case, the temperature to be reached may still be below the temperature of the given individual reactants, and melting may continue to occur because mixtures of different materials are often melted at lower temperatures than any of the components of the pure form mixture It is because it is.

In general, the temperature is preferably slightly lower than the melting point of the reactants having the lowest melting point, but may be such a melting point or slightly higher than such melting point. In a preferred embodiment, the temperature may be within 20 캜 of the melting point, preferably within 10 캜 of the melting point. It has been found that such temperatures are advantageous in terms of metal-organic compound formation when used.

Depending on the conditions of the shear and pressure required during the extrusion process to obtain the desired properties and yield of the metal-organic compound, and the dwell time, the configuration of the screws or screws may be altered. In general, biaxial or other multi-axial arrangement better accommodates the deformation of the configuration, and to a lesser extent in the case of a single-screw extruder. Among others, it is possible to modify the following aspects of the extrusion apparatus or process: the length of the barrel, the length of the barrel: the diameter ratio (L / D ratio), the configuration of the screw element (e.g., The screw rotational speed, the feeding method (starvation feed to flood feeding), the number of extruder passes, etc. These aspects can be used in the extrusion process and in the production Which allows a high degree of control over the metal-organic compound product.

It has been found that the L / D ratio during extrusion is preferably 15/1 or more (i.e., the length is 15x or more than the diameter of the screw). Preferably, the L / D ratio is 20/1 or greater, and in some embodiments, a ratio of 30/1 or greater may be preferred. It has been found that the L / D ratio of 40/1 is very suitable for the formation of metal-organic compounds. This ratio is particularly applicable to biaxial systems, but can also be applied to other extrusion systems.

During extrusion, the mixture is preferably capable of being exposed in at least one period of the dispersed or dispersed mix. In general, the mixture is preferably exposed to at least one period of the dispersed mixture; Dispersive mixing appears to be more aggressive in terms of shear, pressure and heat generation, and is therefore often useful in inducing the formation of co-crystals. In general, it is most preferred that the mixture is exposed to at least one period of each of the distributed and dispersed mixes.

Screws, particularly biaxial or other multi-screw extruders, of the extruder may comprise a number of different elements which determine the conditions under which the material is given during extrusion. It should be noted that these elements are not always "screws" in the strictest sense. That is, they can not include a continuous spiral screw, but the term screw is still used for the assembly, regardless of construction. Generally, a substantial portion of the length of the screw will comprise helical threads, and typically one half or more of its length will include helical threads.

The elements constituting the screw are typically assembled on a shaft to form a complete screw. The shaft typically has a cross-section that prevents rotation of the element relative to the shaft, e.g., a polygon, and in many cases a hexagon. Each element is typically very short compared to the total length of the screw. It is most appropriate to mention the length of the element in relation to the ratio of the diameter of the screw of the extruder.

Helical screw elements are used to transport material through an extruder, which provides relatively low levels of mixing, and application of pressure and shear. The pressure and shear levels applied by such helical elements can be varied, for example, by varying the degree of engagement of such helical elements in a multi-screw extruder and by varying the depth and / or height of such elements. May be in different helical screw types, for example, a forward carrying element, a discharge element or a reverse screw element.

Where stronger mixing and application of shear and pressure are required, this can be achieved by means of a mixing element, in particular a mixing paddle. Mixing paddles typically include leaflet elements, e.g., elliptical or similar shaped elements, which do not include helical threads. The paddles provide a flat mixing surface of the curve. In a twin-screw extruder, one or more corresponding pairs of leaflet elements may be provided on each screw. The laminar elements on one screw are typically rotated 90 degrees (i.e., generally elliptical) with respect to the lobes so that they are rotated and offset relative to the laminar elements on the other screw, and when the element rotates, Are arranged to remain substantially constant during rotation due to the corresponding shape of the paddle pairs or to be separated at narrow intervals which may vary to some extent during rotation. Different degrees of offset can be used for the trilobites, or, if appropriate, for other shapes of mixing elements. The effect of such mixing paddles is to allow the mixture to be applied between pairs of paddles and thus to a relatively strong mixing at high shear and pressure. Also, the flat nature of the mixing surface means that forward transport is not strongly promoted, and thus the mixture will tend to stay in such an element; The forward transport of the mixture is effected by the pressure exerted by the upstream mixture, which is mainly driven by upstream transport of the element, but as will be discussed below, the particular configuration of the mixing element provides some forward transport.

The degree of mixing, and the application of shear and pressure, can be determined by the number and composition of the mixing elements. Distributed mixing is a well-known term in the field of extrusion technology, which means that "distributed mixing is a process of diffusing a minority component throughout the matrix to achieve good spatial distribution matrix in order to achieve good spatial distribution ". Distributed mixing can be achieved by providing a series of mixed (e.g., leaf) elements, with each pair of mixing elements being rotationally offset relative to the preceding pair. That is, this is a stagger angle. Generally, the subsequent mixing element is offset in the same direction as the direction of the helical portion providing the forward transport. Typically, the length of each blending element (e.g., leaflet element) will be at most 0.25 x of the screw diameter, preferably at least 0.125 x of the screw diameter; For example, in the case of a 16 mm diameter screw, each element may have a length of 4 mm. Distributed mixing can be regarded as primarily mixing by rearranging the flow path of the mixture of materials; Essentially, the relatively short length of each mixing element means that the mixture is agitated between the mixing elements, and the level of very limited smearing is relatively low. The amount of rotational offset determines the amount of transport that such a distributed mixing sequence provides and, to some extent, the intensity of the mixing. If the pair is offset from the leading pair by about 10 ° to 45 ° (typically 30 °) in the same direction as the spiral on the feed screw, a significant degree of forward transport is eliminated; An offset of about 46-65 [deg.] (Typically 60 [deg.]) Provides somewhat less transport; An offset of about 75 ° to 90 ° provides significantly less transport, with an offset of 90 ° essentially not providing transport of the mixture.

Dispersive mixing is intense form mixing and provides high levels of shear and pressure to the mixture. Dispersive mixing is a well-known term in the field of extrusion technology, and the term "dispersive mixing " includes the reduction of the size of coherent hydrophobic components such as droplets or clusters of solid particles such as clusters of solid particles or droplets of a liquid. " Dispersive mixing can be achieved when the mixture is compressed and is induced to pass through a long mixing zone that is smeared between the mixing surfaces of the mixing elements. Dispersive mixing may be provided by one or more mixing elements, e. G., Double leaf elements, which provide long regions of the mixing surface without any rotational offset; That is, the long area of the mixing surface may be provided by a relatively long pair of mixing elements (on each screw of the biaxial system) without a substantial rotational offset, or a plurality of There may be a sequential shorter element of. For example, an area of 0.5x or more of the screw diameter at a length comprising the leaf-blend element will provide a dispersive blend without rotational offset. Suitably, the dispersive mixing zone may comprise two or more leaf elements that are not offset relative to each other. That is, they provide a substantially continuous mixing surface. Essentially, a significant aspect of the dispersive blending is that at least a portion of the mixture is limited to being passed through the mixing element between those where the mixture is smeared and subjected to a high degree of pressure and shear, &Lt; / RTI &gt;

It should be noted, however, that the above distributed and dispersed mixed systems are exemplary of systems preferred for use in the present invention. Other methods of achieving distributed or distributed mixing can be considered by those skilled in the art. A discussion of distributed and distributed mixing is provided in Rheology Bulletin Vol. 66, No. 1 (January l997) "Analysis of Mixing in Polymer Processing Equipment" by Ica Manas-Zloczower.

The extrusion apparatus used in the present method is characterized in that the dispersive mixing region (i.e. the region comprising the mixing element) is at least 1/40 of the total length of the screw, preferably at least 1/30 of the total length of the screw, Preferably at least 1/20. Preferably, there is at least one dispersive mixed region, which is at least 0.5 diameter in length. More preferably, there is at least one dispersive mixed region, and the total length of all the dispersed mixed regions is at least 1.5 or more diameters, preferably 2 or more diameters.

In embodiments of the present invention, it is desirable to have both mixed and dispersed mixed regions, i.e., regions containing mixed elements. In a preferred embodiment, such a configuration comprises at least one distributed mixed region followed by at least one dispersed mixed region. In a preferred embodiment of the present invention, at least two distributed mixed regions and at least two dispersed mixed regions are provided. Each of the distribution type mixed regions is at least one diameter in length, more preferably at least 1.5 diameters in length, and these may be two or more diameters in length. Preferably, each dispersive mixed region has a length of at least 0.5 diameter, which may be a length of one or more diameters, and which may be a length of 1.5 or more diameters. Generally, the length of the mixing zone is a total of 5 or more diameters, more preferably the mixing zone is 10 or more diameters.

Generally, it is preferred that half or less of the total screw length of the extrusion system comprises the mixing element, and more typically 2/5 or less, or 1/4 or less of the total screw length, . Of course, the actual ratio may vary depending on the total screw length, and a case where more than half of the total length includes the mixing element can be considered.

및 CCDC로부터 ZIF-8의 시뮬레이션된 PXRD 기록

을 나타낸 것이다.
도 8은 95 rpm에서 1킬로의 시약의 압출로부터 활성화된 압출물의 PXRD 기록

및 CCDC로부터 ZIF-8의 시뮬레이션된 PXRD 기록

을 나타낸 것이다.
도 9는 다양한 속도에서 Cu₃(BTC)₂ 합성으로부터 활성화된 압출물의 PXRD 기록을 나타낸 것이다.
도 10은 킬로 규모의 Cu₃(BTC)₂로부터 활성화된 압출물의 PXRD 기록을 나타낸 것이다.
도 11은 감소된 체류 시간으로 Cu₃(BTC)₂ 합성으로부터 활성화된 압출물의 PXRD 기록을 나타낸 것이다.
도 12는 감소된 체류 시간으로 Cu₃(BTC)₂ 합성으로부터 활성화된 압출물의 PXRD 기록을 나타낸 것이다.
도 13은 ALq₃의 합성된 ALq₃.AcOH

및 상응하는 시뮬레이션된 패턴

의 PXRD 기록을 나타낸 것이다.
도 14는 합성된 [Ni(NCS)₂(PPh₃)₂]

및 상응하는 시뮬레이션된 패턴

의 PXRD 기록을 나타낸 것이다.
도 15는 합성된 [Ni(살렌)]

및 상응하는 시뮬레이션된 패턴

의 PXRD 기록을 나타낸 것이다.
도 16은 실시예 24에 사용된 PTFE 스크류의 사진을 나타낸 것이다.
도 17은 CCDC로부터 얻어진 단축 압출로부터 제조된 ZIF-8

대 ZIF-8의 시뮬레이션된 패턴

의 PXRD 기록을 나타낸 것이다.1 is a schematic diagram showing the basic layout of a twin-screw extruder of Haake Rheomex and ThermoFisher Process.
Figure 2 shows the screw configuration for a Haake Rheomex extruder.
Figure 3 shows the screw configuration for a ThermoFisher Process 11 extruder.
Figure 4 shows a simulated and tested PXRD pattern for the synthesis of ZIF-8 by extrusion.
Figure 5 shows a simulated and tested PXRD pattern for the synthesis of CuBTC by extrusion.
Figure 6 shows the PXRD record of the first extrudate activated from the extrusion of Example 11 at various speeds (55, 75 and 95 rpm).
Figure 7 shows the PXRD record of the extrudate activated from extrusion at 200 &lt; 0 &gt; C (55 rpm)

And simulated PXRD record of ZIF-8 from CCDC

Lt; / RTI &gt;
Figure 8 shows the PXRD record of the activated extrudate from extrusion of 1 kilo of reagent at 95 rpm

And simulated PXRD record of ZIF-8 from CCDC

Lt; / RTI &gt;
Figure 9 shows a PXRD record of an activated extrudate from Cu ₃ (BTC) ₂ synthesis at various rates.
Figure 10 shows a PXRD record of an activated extrudate from kilo-scale Cu ₃ (BTC) ₂ .
Figure 11 shows the PXRD record of an activated extrudate from Cu ₃ (BTC) ₂ synthesis with reduced residence time.
Figure 12 shows the PXRD record of an activated extrudate from Cu ₃ (BTC) ₂ synthesis with reduced residence time.
13 is ALq ₃ synthesized ALq ₃ .AcOH of

And the corresponding simulated pattern

&Lt; / RTI &gt;
Fig. 14 is a graph _{showing the relationship} between the synthesized [Ni (NCS) ₂ (PPh3) ₂ ]

And the corresponding simulated pattern

&Lt; / RTI &gt;
Fig. 15 is a graph showing the relationship between the synthesized [Ni (salen)]

And the corresponding simulated pattern

&Lt; / RTI &gt;
16 is a photograph of the PTFE screw used in Example 24. Fig.
FIG. 17 is a graph showing the results of ZIF-8 produced from uniaxial extrusion obtained from CCDC

Simulated Patterns vs. ZIF-8

&Lt; / RTI &gt;

Experimental Method

General mode

General mode: Two different model extruders were used: a Haake Rheomex OS PTW16 dynamic twin screw extruder and a ThermoFisher Process 11 dynamic twin screw extruder.

Figure 1 is a schematic diagram showing the basic layout of both extruders. The lower part of the barrel consists of a single piece, while the upper part is assembled into six sections. Some sections contain plugs that can be removed so that a feeding neck can be inserted. The plug is circular and shows two Allen-key screws that are secured to and removed from the barrel. The screw is not shown in this diagram so that the cross-sectional shape of the empty barrel can be seen.

Haake Rheomex

For the Haake Rheomex extruder, a metering feed system was used. This consists of a simple funnel hopper that drops the material into a single screw, which then transports the material to the opening and drops it into the extruder barrel. This device has a screw diameter of 16 mm and a screw length to diameter (L / D) ratio of 25: 1. It features five temperature-controlled barrel zones and a divided screw configuration that allows fine control of the extrusion process. F30 (x3), A90 (x4), FS (x3), FS (1/2), F30 (x3), and F30 , F60 (x1), FS (x3), F30 (x3), F60 (x3), F30 (x6), FS (x3), EXT. A description of each screw element is contained in the user manual for such equipment. The screw configuration for the Haake Rheomex extruder can be shown in Fig.

ThermoFisher  Process 11 extruder

The ThermoFisher Process 11 extruder used a micro-biaxial feeder for weight. Its hopper was a sealed cylinder and had three rotatable arms on an axis spaced 120 [deg.] To each other. This allowed continuous agitation of the powder before feeding, which prevents the particles from sticking together. The screw configurations used throughout all the experiments in these devices are FS (x9), F30 (x5), F60 (x3), A90 (x4), FS (x7), F60 (x4), A90 (x8), FS (x7), and EXT. A description of each screw element is contained in the user manual for such equipment. The screw configuration for ThermoFisher Process 11 can be shown in Fig.

The cleaned extruder was preheated to the selected processing temperature. A barrel temperature profile was used, typically ranging from a cooled feed zone to a maximum intermediate along the barrel and decreasing toward the die end. For the purpose of this experiment, the extruder was driven without a die. The extruder screw rotation speed was set as follows: A wide range of speeds up to 1000 rpm could be achieved by the extruder used here. A typical screw rotational speed was set at 40 to 70 rpm. The premixed combination of the metal salt and the organic ligand reactant was then introduced into the feed hopper of the extruder. For small batch sizes, manual dosing may appear appropriate (typically 10-200 g). For larger batch sizes, a weighing or bulk feeder system may be used more appropriately. The extruded product was then collected in a powder, sticky mass or molten form depending on the constituents and the set operating conditions in the ejector of the screw. The collected materials were then analyzed for metal organic compound formation.

During the course of the experiment, the following parameters can be adjusted:

· Setting temperature

· Screw rotation speed

· Throughput

Screw design (ie, degree of distribution and dispersion mixing)

Number of passes through the extruder

· Precursor ratio

· Type of added solvent

· Amount of solvent added

Process checks that removed the top of the barrel to see the reacting material showed no evidence of formation of the liquid phase.

Example  1 - Zn MOF ( ZIF -8)

By mixing 40 g of [ZnCO ₃ ] ₂ [Zn (OH) ₂ ] ₃ and 60 g of C ₄ H ₆ N ₂ (HMIM) (molar ratio 10: 1) in a cup, basic zinc carbonate and 2-methylimidazole &Lt; / RTI &gt; The Haake Rheomex extruder was used in the specified screw configuration consisting mainly of a forward feed element and a small dispense mixing zone. The barrel of the extruder was at room temperature. The physical mixture was slowly fed to the extruder at a rate of 5 g / min and the screw rotated at 55 rpm. The finely agglomerated product was collected at the outlet of the extruder and then recycled four more times to the extruder. On the fourth pass through the extruder, 8 mL of MeOH was also fed to the extruder.

The resulting powder (substance 1) was collected. A sample of 1 g of substance 1 was subjected to powder X-ray diffractometric (PXRD) characterization. The X-ray diffraction pattern of substance 1 was sufficiently similar to that calculated for the previously known metal-organic structure ZIF-8, suggesting that the reaction between the precursors was made to produce the metal organic structure ZIF-8. Comparative PXRD data was simulated from monocrystalline X-ray diffraction data in the Cambridge Structural Database.

A sample of 2.5 g of substance 1 was washed, immersed in 100 mL of MeOH for 20 minutes, activated and placed in an oven at 150 DEG C for 2 hours. Thereafter, the sample was subjected to BET surface area analysis, which provided a very high surface area of 1417 m ² / g.

Figure 4 shows the PXRD patterns (simulated and tested) obtained for material 1 along with the theoretical PXRD pattern for the known metal organic structure ZIF-8.

Based on the above method, it is possible to use other metals, such as ZIF-67 (by reaction of 2-methylimidazole with cobalt hydroxide) or other organic molecules such as ZIF-7 by reaction of zinc and benzimidazole imidazole), Cu (isopropyl nicotinate) ₂ (isonicotinic acid and Cu (OAc) by reaction of the .H ₂ O), Mg (isopropyl nicotinate) ₂ (Mg (OH) by the reaction of ₂ and isonicotinic acid), Li (isopropyl nicotinate) (by the reaction of LiOH and isonicotinic acid), and Mn (isopropyl nicotinate) ₂ (Mn (OAc) by reaction of ₂ with isonicotinic acid) Can be produced.

Example  2 - Cu MOF ( CuBTC )

A physical mixture of copper acetate monohydrate and 1,3,5-benzenetricarboxylic acid was prepared by mixing 58.8 g Cu (OAc) ₂ H ₂ O and 41.4 g H ₃ BTC (molar ratio 3: 2) in the cup . The Haake Rheomex extruder was used in the specified screw configuration consisting mainly of a forward feed element and a small dispense mixing zone. The barrel of the extruder was at room temperature. The physical mixture was slowly fed to the extruder at a rate of 5 g / min and the screw rotated at 55 rpm. The finely agglomerated product was collected at the outlet of the extruder and then recycled two more times to the extruder. At the second pass through the extruder, 20 mL of MeOH was also fed to the extruder.

The resulting powder (substance 2) was collected. A sample of 1 g of Substance 2 was subjected to powder X-diffraction (PXRD) characterization. The X-ray diffraction pattern of substance 2 was sufficiently similar to that calculated for the previously known metal-organic construct CuBTC (HKUST-1), which allows the reaction between the precursors to generate the metal organic structure CuBTC (HKUST-1) . Comparison PXRD data was simulated from monocrystalline X-ray diffraction data in the Cambridge Structural Database.

A sample of 2.5 g of Substance 2 was washed, immersed in 100 mL of EtOH for 20 minutes to activate, and then placed in an oven at 150 DEG C for 2 hours. Thereafter, the sample was subjected to BET surface area analysis, which provided a very high surface area of 706 m ² / g.

Figure 5 shows the PXRD pattern (simulated experiment) obtained for material 2 with the theoretical PXRD pattern for the known metal organic structure CuBTC (HKUST-1).

Based on the above method, an alternative metal, such as Fe (BTC) (by reacting H ₃ BTC with Fe (OAc) ₃ ) or La (BTC) (by reacting La ₂ (CO ₃ ) ₃ with H ₃ BTC) , or alternatively an organic linker, for example, MOF-74 (Zn) (by reacting a basic zinc carbonate and 2,5-dihydroxy terephthalic acid), MOF-74 (Mg) (Mg (OH) 2 and 2,5- by reacting the dihydroxy-terephthalic acid), by reacting a MOF-74 (Co) (Co (OH) 2 and 2,5-dihydroxy terephthalic acid), MOF-74 (Fe) (Fe (OAc) 2 and 2, 5-dihydroxyterephthalic acid), MIL-53 (by reacting Al (OH) (OAc) ₂ with terephthalic acid).

Example  3 - 8 - Hydroxyquinoline  Zn complex

Zn-quinolinate complex was synthesized as described below. The complexes were synthesized from zinc acetate dihydrate and from basic zinc carbonate. HAAKE Rheomex PTW16 OS extruder and ThermoFisher Process 11 extruder were used as shown in the experimental section below.

Zinc compound 1 Zinc compound 2

The structure of the Zn-quinolinate complex was obtained by extrusion, which is mentioned in Example 3.

Example  3 (i) - Synthesis from zinc acetate dihydrate

Method A ( Haake Rheomex  16):

Both reactants were pre-milled in a vibrating ball mill and sowed with an industrial standard (355 μm mesh). The zinc acetate dihydrate (43 g, 1.95 mol) was manually mixed with 8-hydroxyquinoline (57 g, 0.393 mol) for 5 minutes. The mixture was placed in a hopper and fed to the extruder barrel at a rate of about 3 g / min with a metering feed screw. The material was manually fed at a rate of about 3 g / min. The material was extruded at 55 rpm without heating the barrel and the yellow / lime green material was collected. Analysis by PXRD showed that the product consisted of a mixture of products (1) and (2).

Method B ( ThermoFisher  Process 11):

8-Hydroxyquinoline was manually pre-milled in large pestle and mortar bowls to match the diameter of the particles to the diameter of the zinc salt (1-3 mm). The zinc acetate dihydrate (43 g, 1.95 mol) was manually mixed with 8-hydroxyquinoline (57 g, 0.393 mol) for 5 minutes. The mixture was placed in a hopper and fed to the extruder barrel at an exact speed of 1.33 g / min. The hopper had an internal mechanical stirrer, and a feeder for biaxial weights. The material was extruded at 200 rpm at barrel temperature set to 50 &lt; 0 &gt; C. Homogeneous green matter was collected. Analysis by PXRD showed that the product consisted of a mixture of products (1) and (2).

Method C ( ThermoFisher  Process 11):

Both reactants were pre-milled in a vibrating ball mill and squeezed into an industrial standard (355 μm mesh). The zinc acetate dihydrate (43 g, 1.95 mol) was manually mixed with 8-hydroxyquinoline (57 g, 0.393 mol) for 5 minutes. The mixture was placed in a hopper and fed to the extruder barrel at an exact speed of 1.33 g / min. The hopper contained a mechanical mixer, which prevented agglomeration of the mixture and kept the mixture as a free-flowing powder. A feeder for biaxial weights designed for powder feed was used. The material was extruded at 200 rpm at barrel temperature set to 50 &lt; 0 &gt; C. The homogeneous green material was collected. Analysis by PXRD showed that the product consisted of a mixture of products (1) and (2).

Example  3 (ii) - Basic From zinc carbonate  synthesis

Method A ( Haake Rheomex  16):

8-Hydroxyquinoline was pre-milled in a vibrating ball mill and both reactants sieved (355 um mesh). Basic zinc carbonate (20.55 g, 0.0374 mol) was added to 8-hydroxyquinoline (54.44 g, 0.375 mol) and manually mixed for 5 minutes. The mixture was placed in a hopper and fed to the extruder barrel at a rate of about 3 g / min with a metering feed screw. The material was extruded at 200 rpm at barrel temperature set to 50 &lt; 0 &gt; C. The initial 5-10 g of pale yellow powder was collected and then the mustard yellow colored material was collected. Analysis by PXRD indicated that this was the product (1).

Method C ( ThermoFisher  Process 11):

The 8-hydroxyquinoline reactant was pre-milled in a vibrating ball mill and both reactants were sieved (355 um mesh). Basic zinc carbonate (20.55 g, 0.0374 mol) was added to 8-hydroxyquinoline (54.44 g, 0.375 mol) and manually mixed for 5 minutes. The mixture was placed in a hopper and fed to the extruder barrel at an exact speed of 1.33 g / min. The hopper contained a mechanical mixer, which prevented agglomeration of the mixture and kept the mixture as a free-flowing powder. A feeder for biaxial weights designed for powder feed was used. The material was extruded at 200 rpm at barrel temperature set to 50 &lt; 0 &gt; C. Approximately 5-10 g of pale yellow powder was collected, and the mustard-yellow colored material was collected. Analysis by PXRD indicated that this was the product (1).

On the basis of the embodiment, Al (8-quinolinyl _{carbonate) 3 (Al (OH) (} OAc) 2 and by reaction of the 8-hydroxyquinoline) or Mg (8-quinolinyl carbonate) ₂ (Mg ( OH) ₂ and 8-hydroxyquinoline) can be prepared.

Table 1

Example  4 to 10

In the following Examples 4 to 10, HAAKE RHEOMEX PTW16 OS extruder was used. The screw speed was set at 55 rpm. The effect of temperature on the synthesis of MOF was evaluated by increasing the temperature of the five heated zones of the barrel from room temperature (25 占 폚) to 150 占 폚. The reagents were premixed and then fed manually using the first feed port at an addition rate of about 5 g / min. The effect of liquid-assisted milling was evaluated by manually adding anhydrous MeOH to the solid mixture. MOF was activated with anhydrous EtOH, MeOH or H ₂ O, as described below. The solid product was recovered by vacuum filtration and dried in a Carbolite PF60 furnace (Serial No. 20-601895) at 150 ° C for 2 h.

Example  4 (i) - Cu ₃ (BTC) ₂ :

In the cup, 41.05 g Cu (OH) ₂ (0.42 mol) and 58.95 g 1,3,5-benzenetricarboxylic acid (0.28 mol) were premixed. 30 mL of MeOH was added to the mixture and the resulting solids were passed through an extruder at room temperature. Finally, 30 mL additional MeOH was added to the mixture and the solids were extruded a second time at room temperature. Formation of CuBTC was confirmed by XRD pattern of the extruded material only for the material extruded with only 30 mL of MeOH. Activation of CuBTC was performed by washing 1 g of blue MOF with 40 mL of anhydrous ethanol for 20 min (x 3). The BET analysis confirmed the high surface area of the activated product (1324 m ² / g).

Example  4 (ii) - using copper acetate CuBTC  Alternative Synthesis:

58.8 g of Cu (OAc) ₂ ? H ₂ O (0.30 mol) and 41.2 g of 1,3,5-benzenetricarboxylic acid (0.20 mol) were premixed in the cup. The non-solvent mixture was passed through the extruder at room temperature while 20 mL of MeOH was added at a rate of 1 mL / min using a second feed port. Finally, the mixture was passed through the extruder one time without further addition of any MeOH. XRD analysis of the extruded material confirmed the formation of CuBTC MOF. BET analysis of the product activated with anhydrous ethanol confirmed the high surface area of MOF (706 m ² / g).

Example  5 (i) - ZIF Synthesis of -8:

30.76 g of [ZnCO ₃ ] ₂ [Zn (OH) ₂ ] ₃ (0.056 mol) and 69.24 g of 2-methylimidazole (0.84 mol) were premixed in the cup. Thereafter, a solid sample was passed through the extruder at 150 占 폚. The solid sample was then passed twice through the extruder at 150 占 폚. The formation of ZIF-8 was confirmed by the XRD pattern of the extruded material only for the once extruded material. Activation of the sample was carried out by washing 2.5 g of ZIF-8 with 20 mL (x 3) of 50 mL of methanol to remove the unreacted excess of 2-methylimidazole.

Example  5 (ii) - ZIF Synthesis of -8:

An alternative synthesis of ZIF-8 at room temperature was also studied. Liquid-assisted grinding (LAG) to methanol was performed. The same solid mixture was passed through an extruder while the second port was used to add 7 mL of MeOH. Finally, the solid mixture was passed through the extruder three times at room temperature. XRD analysis confirmed the formation of MOF and confirmed the high surface area of ZIF-8 (1614 m ² / g) by BET analysis of the activated product.

** Excess 2-methylimidazole was used in the synthesis of ZIF-8 because it was found that lower surface area was obtained when stoichiometric amounts were used in the previous work. Stoichiometric amount (40 g of _{[ZnCO 3] 2 [Zn (} OH) 2] 3 (0.073 mol) and the 2-methyl imidazole of 60 g (0.730 mol)) by extrusion at 150 ℃ using the ZIF The synthesis of -8 produced ZIF-8 with a surface area of 1253 m ² / g.

Example  6 - ZIF -67:

36.15 g of Co (OH) ₂ , mp 168 ° C. (0.39 mol) and 63.85 g of 2-methylimidazole, mp 144 ° C. (0.78 mol) were pre-mixed in the cup and the solventless mixture was fed to the extruder I passed it. Thereafter, the solid product was again extruded at 150 캜 twice. The XRD pattern of the extruded material (only for the extruded product) showed a characteristic diffraction peak of ZIF-67 confirming the formation of MOF.

ZIF-67 was activated by washing 2.5 g of purple MOF with 50 mL of MeOH for 20 min (x 3). The XRD pattern of the activated product did not show any significant difference compared to the material obtained directly from the extruder. The BET analysis of the activated product confirmed its high surface area (1232 m ² / g).

 It should be noted that the characteristic diffraction peaks of ZIF-67 were not present in the XRD pattern of the extruded product when the same solid mixture was extruded at room temperature. However, when activated with MeOH, a diffraction peak corresponding to the MOF confirming the formation of ZIF-67 was detected.

Example  Synthesis of 7-Mg-MOF-74:

37.06 g of Mg (OH) ₂ (0.64 mol) and 62.94 g of 2,5-dihydroxybenzene-1,4-dicarboxylic acid (0.32 mol) were premixed in the cup. 10 mL of MeOH was added to the solid mixture with stirring with a spatula and the resulting solids were passed through an extruder at room temperature. An additional 10 mL of MeOH was then added to the extruded solids with stirring with a spatula and the resulting mixture was passed twice through an extruder at room temperature. Finally, an additional 10 mL of MeOH was added to the solid mixture and the resulting solid powder was passed through the extruder three times at room temperature. PXRD analysis of the product confirmed the formation of Mg-MOF-74. Mg-MOF-74 was activated by washing 1 g of yellow MOF with 60 mL of degassed MeOH for 18 h and filtered under N2. The BET analysis of the activated product confirmed its high surface area (684 m ² / g).

Example  Synthesis of 8-Co-MOF-74:

48.41 g of Co (OH) ₂ (0.52 mol) and 51.59 g of 2,5-dihydroxybenzene-1,4-dicarboxylic acid (0.26 mol) were premixed in the cup. 10 mL of MeOH was added to the cup containing the solid mixture while stirring with a spatula, and then the solid mixture was passed through an extruder at room temperature. An additional 10 mL of MeOH was then added to the mixture with stirring with a spatula, and the resulting solids were passed twice through the extruder at room temperature.

Finally, an additional 10 mL of MeOH was added to the solid mixture and the resulting solids were passed through the extruder three times at room temperature. XRD analysis of the product confirmed the formation of Co-MOF-74. Activation of MOF was performed by washing 2.5 g of Co-MOF74 with 50 mL of MeOH for 20 min (x3). However, the XRD pattern of the activated MOF showed no significant difference compared to the material obtained directly from the extruder.

Example  Synthesis of 9-Zn-MOF-74:

52.48 g of [ZnCO ₃ ] ₂ [Zn (OH) ₂ ] ₃ (0.096 mol) and 47.52 g of 2,5-dihydroxybenzene-1,4-dicarboxylic acid (0.240 mol) were premixed in the cup. 10 mL of MeOH was added to the cup containing the solid mixture with stirring with a spatula and the resulting solids were passed through an extruder at room temperature. An additional 10 mL of MeOH was then added to the solids with stirring with a spatula, and the solid mixture was passed twice through the extruder at room temperature. Finally, an additional 10 mL of MeOH was added to the solids with stirring with a spatula and the resulting solids passed through the extruder three times at room temperature. XRD analysis of the product confirmed the formation of Zn-MOF-74. MOF activation was performed by washing 2.5 g MOF with 50 mL MeOH for 20 min (x3). However, the XRD pattern of the activated MOF showed no significant difference compared to the material obtained directly from the extruder.

Example  10 - Al (OH) Fumarate  synthesis:

The cup was premixed with 74.48 g Al ₂ (SO ₄ ) ₃ .18H ₂ O (0.11 mol), 25.94 g fumaric acid (0.22 mol) and 26.64 g NaOH pellets (0.66 mol) Lt; / RTI &gt; The solids were then passed twice through the extruder at room temperature without any solvent added. Finally, the solids were passed through the extruder three times at room temperature without any solvent added. The XRD pattern of the material passed twice and three times through the extruder showed characteristic diffraction peaks of Al (OH) fumarate confirming the formation of MOF. However, Na ₂ SO ₄ (formed as a byproduct) was also detected on the XRD pattern. MOF activation was performed by washing 1 g of product with 30 mL of H ₂ O for 20 min (x 3). The XRD pattern of the activated product showed a diffraction peak corresponding to Al (OH) fumarate, confirming that only Na ₂ SO ₄ was removed. By BET analysis, the high surface area of the activated Al (OH) fumarate MOF produced by extrusion was confirmed (1010 m ² / g).

Note that when passing the same solid mixture through an extruder at 150 ° C, a characteristic diffraction peak of aluminum MOF was also detected for the once extruded material.

** Further work has shown that the process can be optimized. A higher feed rate (10 g / min) was achieved by increasing the screw speed to 95 rpm and using NaOH pearl. The higher surface area of the MOF produced by the BET analysis of the activated material was also confirmed (945 m ² / g for 14 g activated product), even when activated on a larger scale.

 Example 11 - Synthesis of ZIF-8 at 150 &lt; 0 &gt; C:

Basic zinc _{carbonate, [ZnCO 3] 2 · [} Zn (OH) 2] 3 (30.81 g, 0.056 mol) and 2-methylimidazole were mixed physically with imidazole (69.18 g, 0.84 mol) (molar ratio 1:15 ). It was manually fed to Haake Rheomex OS PTW16 at speeds ranging from 55, 75 and 95 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was set at 150 占 폚. From each experiment, the beige melted extrudate, which solidified very quickly upon cooling to room temperature, was collected. The extrudate was extruded an additional two times at the same rate, but the second extrusion was very difficult to feed due to any shaped 'clumps' formed during cooling. The throughput was measured from the first extrusion, which is outlined in Table 2.

Table 2

The PXRD of the ZIF-8 extrudate as synthesized was sufficiently similar to the simulated PXRD pattern of ZIF-8 obtained from single crystal X-ray diffraction data in the Cambridge structure database. The PXRD record showed a complete response after the first extrusion.

Activation was carried out by stirring in HPLC grade methanol (400 mL) at room temperature for 2 hours. The suspension was filtered to give a white solid. This was added to HPLC methanol at room temperature for an additional 2 hours and filtered. Thereafter, the white solid was dried in an oven at 150 캜 for 2 hours. The PXRD analysis provided a record that matched the record of the simulated PXRD pattern of ZIF-8 obtained from single crystal X-ray diffraction data in the Cambridge structure database (FIG. 6). TGA and CHNS analysis also showed complete reaction at each speed after one extrusion.

Example  At 12-200 ° C ZIF Synthesis of -8:

Basic zinc _{carbonate, [ZnCO 3] 2 · [} Zn (OH) 2] 3 (30.81 g, 0.056 mol) and 2-methylimidazole were mixed physically with imidazole (69.18 g, 0.84 mol) (molar ratio 1:15 ). This was manually fed to Haake Rheomex OS PTW16 at a screw speed of 95 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was set at 200 占 폚. From each experiment, the beige melted extrudate, which solidified very quickly upon cooling to room temperature, was collected. A total of 4.5 minutes was required to extrude the reagents and collect the extrudate, and accordingly the throughput was determined to be 1.33 kg / hr. Only one extrusion performed as a previous experiment showed that a complete reaction was obtained after one extrusion. Due to the high temperature of the experiment, 2-methylimidazole was observed to form a resistive polymer covering the surface of the screw which was difficult to remove.

The PXRD of ZIF-8 as synthesized was sufficiently similar to the simulated PXRD pattern of ZIF-8 obtained from single crystal X-ray diffraction data in the Cambridge structure database.

Activation was carried out by stirring in HPLC grade methanol (400 mL) at room temperature for 2 hours. The suspension was filtered to give a white solid. This was added to HPLC methanol at room temperature for an additional 2 hours and filtered. Thereafter, the white solid was dried in an oven at 150 캜 for 2 hours. The PXRD analysis provided a record that matched the record of the simulated PXRD pattern of ZIF-8 obtained from the single crystal X-ray diffraction data in the Cambridge structure database (FIG. 7).

Example  13-kilobyte ZIF Synthesis of -8:

The basic zinc carbonate, [ZnCO ₃ ] _2. [Zn (OH) ₂ ] ₃ (308.1 g, 0.56 mol) and 2-methylimidazole (691.8 g, 8.4 mol) were physically mixed together in one batch Molar ratio 1:15). This was manually fed into a Haake Rheomex extruder at a screw speed of 95 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was set at 200 占 폚. A molten extrudate was produced, which was collected in five approximately identical batches to confirm homogeneity. The reagent was extruded only once.

The PXRD of the extrudates (batch A-E) as synthesized exhibited homogeneity and all the records were very similar to the records of the simulated PXRD patterns obtained from the single crystal X-ray structures provided by the Cambridge Structural Database.

Activation was performed by stirring 5 g of the sample in 40 mL of HPLC grade methanol for 2 hours. This was filtered to give a white solid which was immersed in the solvent and stirred for an additional 2 hours. The suspension was filtered and the resulting solids were oven-dried at 150 &lt; 0 &gt; C for 2 hours. The PXRD of the activated product was very similar to the simulated PXRD record obtained for ZIF-8 (Figure 8).

Example  14 - Cu ₃ (BTC) ₂ of  synthesis:

Copper (II) hydroxide (0.43 mol, 42.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (58.0 g, 0.286 mol) were physically mixed together (molar ratio 3: 2) . HPLC grade methanol was slowly added and the mixture was stirred. Heat was generated from the addition of solvent, and the mixed solids became darker green. It was fed manually to a Haake Rheomex extruder at screw speeds ranging from 55, 75, 95, 115, 135, 155 and 250 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was maintained at room temperature. A light blue extrudate paste was produced, which formed a large clump after the first extrusion. It was disrupted and an additional 20 mL of MeOH was added to the extrudate. This was fed to the extruder twice to produce a blue powder which was extruded three times without further addition of MeOH. The throughput from the first extrusion was measured and is outlined in Table 3.

Table 3

The PXRD of the extrudate as synthesized suggests a complete reaction because the record is very similar to the simulated record generated from the single crystal X-ray diffraction data provided by the Cambridge Structural Database. After the first extrusion, it may appear to be a complete reaction.

Extruded  Activation:

Four methods were used to activate the Cu ₃ (BTC) ₂ extrudate.

Method 1: 8 mL of anhydrous ethanol per 1 g of extrudate was used. The extrudate was immersed in absolute ethanol and sonicated in an ultrasonic cleaning bath for 20 minutes. The suspension was filtered. This process was repeated two more times, but blue color was observed to darken. The solid product was oven-dried at 150 DEG C for 2 hours. A dark purple solid was produced.

Method 2: 8 mL of anhydrous ethanol per 1 g of extrudate was used. The extrudate was immersed in absolute ethanol and stirred at room temperature for 20 minutes. Thereafter, the suspension was filtered and the process was repeated two more times. Again, it can be observed that the blue color becomes darker. The solid was oven-dried at 150 &lt; 0 &gt; C for 2 hours to give a dark purple solid.

Method 3: 8 mL of industrial alcohol (99.9% ethanol) per 1 g of extrudate was used. The extrudate was immersed in absolute ethanol and sonicated in an ultrasonic cleaning bath for 20 minutes. The suspension was filtered. This process was repeated two more times, but blue color was observed to darken. The solid product was oven-dried at 150 DEG C for 2 hours. A dark purple solid was produced.

Method 4: 8 mL of industrial alcohol (99.9% ethanol) per 1 g of extrudate was used. The extrudate was immersed in absolute ethanol and stirred at room temperature for 20 minutes. Thereafter, the suspension was filtered and the process was repeated two more times. Again, it can be observed that the blue color becomes darker. Oven-dried at 150 &lt; 0 &gt; C for 2 hours to give a dark purple solid.

The PXRD of this activated product provided a record that matched appropriately to that of the simulated PXRD record obtained from the Cambridge structure database (FIG. 9).

Example  15 - Cu ₃ (BTC) ₂ of  Synthesis (various methanol % wt ):

Copper (II) hydroxide (0.43 mol, 42.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (58.0 g, 0.286 mol) were physically mixed together (molar ratio 3: 2) . Various amounts of HPLC grade methanol (40 mL, 60 mL, 80 mL, 100 mL and 120 mL) were added slowly to each experiment and the mixture was stirred. Heat was generated from the addition of the solvent, and the mixed solids became darker green in the mixture containing 60 mL or more of methanol. This was fed manually to a Haake Rheomex extruder having a screw length: diameter ratio of 25 twin screw extruders at 135 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was maintained at room temperature. A pale blue powder extrudate was produced, except that a green extrudate was produced in an experiment with 40 mL of methanol. PXRD of the extrudate as synthesized upon addition of 60 - 120 mL of methanol suggests a complete reaction. Experimental PXRD with 40 mL of methanol showed the presence of Cu (OH) ₂ and was therefore not successful.

Activation was performed via outlined method 2 to produce a deep purple powder from experiments involving 60 mL or more of the solvent. The PXRD of the activated product was sufficiently similar to the simulated PXRD record provided by the Cambridge Structural Database.

Example  16 - Cu ₃ (BTC) ₂ of  Synthetic (various industrial Alcohol % wt ):

Copper (II) hydroxide (0.43 mol, 42.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (58.0 g, 0.286 mol) were physically mixed together (molar ratio 3: 2) . Various amounts of industrial alcohol (99.9% ethanol) (40 mL, 60 mL, 80 mL, 100 mL, and 120 mL) were slowly added to each experiment and the mixture was stirred. Heat was generated from the addition of the solvent, and the mixed solids became darker green in the mixture containing 60 mL or more of methanol. It was manually fed to ThermoFisher Process 11 at a rate of 135 rpm skew. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was maintained at room temperature. A pale blue powder extrudate was produced, but a green extrudate was produced in an experiment using 40 mL of industrial alcohol.

PXRD of extrudates as synthesized upon addition of 60 - 120 mL of industrial alcohol suggests a complete reaction. Experimental PXRD with 40 mL of industrial alcohol showed the presence of Cu (OH) ₂ and thus was not successful.

Activation was performed via outlined method 4 to produce a deep purple powder from experiments involving 60 mL or more of the solvent. The PXRD of the activated product was sufficiently similar to the simulated PXRD record provided by the Cambridge Structural Database.

Example  17-kilo-sized Cu ₃ (BTC) ₂ of  synthesis:

Copper (II) hydroxide (4.30 mol, 420.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (580.0 g, 0.2.86 mol) 2). 400 mL of methanol was added to the reagent mixture, heat was generated from the addition of the solvent, and the mixed solids became darker green. This was manually fed into a Haake Rheomex extruder at a screw speed of 135 rpm. The screw consisted mainly of a forward carrying section and two kneading sections. The barrel of the extruder was maintained at room temperature. A pale blue powder extrudate was produced and collected in five batches for homogeneity testing. The PXRD of the extrudates (batch AE) as synthesized exhibited homogeneity, and all records were very similar to the recorded simulated patterns obtained from the single crystal X-ray structures provided by the Cambridge Structural Database.

After carrying out 50 g of activation via Method 2, a dark purple solid was produced after oven-drying at 50 DEG C for 2 hours. The PXRD of the activated product produced a record that matched the simulated record obtained from the Cambridge structure database (Figure 10).

Example  18 - Stay time Reduced Cu ₃ (BTC) ₂ of  synthesis:

Copper (II) hydroxide (0.43 mol, 42.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (58.0 g, 0.286 mol) were physically mixed together (molar ratio 3: 2) . 80 mL of industrial alcohol (99.9% ethanol) was slowly added and the mixture was stirred. Heat was generated from the addition of solvent, and the mixed solids became darker green in the mixture. It was manually fed into a ThermoFisher Process 11 parallel twin screw extruder at screw speeds of 155 and 250 rpm. The screw consisted mainly of a forward carrying section and only one kneading section. The retention time was measured to be about 12 seconds at 155 rpm and about 6 seconds at 250 rpm. The barrel of the extruder was maintained at room temperature. A pale blue extrudate powder was produced. The PXRD of the extrudates as synthesized suggests a complete response in both cases since the record is very similar to the simulated record generated by the Cambridge structure database. Activation was performed via Method 4 to produce a deep purple powder in both cases. The PXRD of the activated product was sufficiently similar to the simulated PXRD record provided by the Cambridge Structural Database (Figure 11).

Example  19 - Time to stay Reduced Cu ₃ (BTC) ₂ of  synthesis:

Copper (II) hydroxide (0.43 mol, 42.0 g), Cu (OH) ₂ and benzene-1,3,5-tricarboxylic acid (58.0 g, 0.286 mol) were physically mixed together (molar ratio 3: 2) . 80 mL of industrial alcohol (99.9% ethanol) was slowly added and the mixture was stirred. Heat was generated from the addition of solvent, and the mixed solids became darker green. It was manually fed into a ThermoFisher Process 11 extruder at screw speeds of 155 and 250 rpm. The mixture was fed into the last conveying section of the screw. The retention time was about 3-4 seconds at 155 rpm and about 1-2 seconds at 250 rpm. The barrel of the extruder was maintained at room temperature. A pale blue extrudate powder was produced. The PXRD of the extrudates as synthesized suggests a complete response in both cases since the record is very similar to the simulated record generated by the Cambridge structure database. Activation was carried out via Activation Method 4 to produce a deep purple powder in both cases. The PXRD of the activated product was sufficiently similar to that of the simulated PXRD provided by the Cambridge Structural Database (Figure 12).

Example  21 - Alq . AcOH  synthesis:

Basic aluminum diacetate (8.1 g, 0.049 mol) and 8-hydroxyquinoline (22.65 g, 0.156 mol) were physically mixed together (molar ratio 1: 3). This was manually fed into the ThermoFisher Process 11 extruder at a screw speed of 55 rpm (residence time of about 1.5 - 2 minutes). A dark yellow solid was formed. The PXRD of the extrudate as synthesized suggests a complete response in both cases since the record is very similar to the simulated record produced by the Cambridge structure database (Figure 13). Excess acetic acid was removed by heating at 200 &lt; 0 &gt; C for 2.0 h to yield a light yellow solid.

Example  22 - [ Ni (NCS) ₂ (PPh ₃ ) ₂ ]:

Nickel (II) thiocyanate (5 g, 0.028 mol) and triphenylphosphine (15 g, 0.0572 mol) were physically mixed together (molar ratio 1: 2). To this was added 0.4 equivalents of HPLC grade methanol (0.0112 mol, 0.57 mL). The paste was manually fed into the ThermoFisher Process 11 extruder at a screw speed of 55 rpm (residence time of about 1.5 - 2 minutes). An orange solid was produced. The PXRD of the extrudate as synthesized suggests a complete response in both cases since the record is very similar to the simulated record generated by the Cambridge structure database (Fig. 14).

Example  23 - [ Ni ( Salen )]:

(9.27 g, 0.037 mol) and salen H ₂ (2,2 '- [1,2-ethanediylbis [(E) -nitrilomethylidine]] bis- 0.037 mol) were physically mixed together (molar ratio 1: 1). To this was added 0.3 equivalents of HPLC grade methanol (0.0111, 0.449 mL). The paste was manually fed into the ThermoFisher Process 11 extruder at a screw speed of 55 rpm (residence time of about 1.5 - 2 minutes). A red brick solid was produced. The PXRD of the extrudate as synthesized suggests a complete response in both cases since the record is very similar to the simulated record produced by the Cambridge structure database (Fig. 15).

Example  Kilo-scale through a 24-screw extruder ZIF Synthesis of -8:

The basic zinc carbonate, [ZnCO ₃ ] _2. [Zn (OH) ₂ ] ₃ (308.1 g, 0.56 mol) and 2-methylimidazole (691.8 g, 8.4 mol) were physically mixed together in one batch Molar ratio 1:15). This was done at a rate of 30 rpm and at a rate of 25 l / d. Were fed manually into a Collin E 25M single-screw extruder. A constantly increasing root diameter 25 mm diameter PTFE screw was used. The screw consisted essentially of a carrying section and a short kneading section in the last section. Fig. 16 shows a PTFE screw used in experiments in which a constantly increasing root diameter (upper image) and a kneading section (lower image) are emphasized. There are five zones, each of which constitutes a barrel, at different temperatures, and Zone 1, i.e., the feed zone, was maintained at 30 ° C. Zone 2 was maintained at 50 占 폚, Zone 3 was maintained at 130 占 폚, and the last two zones were maintained at 150 占 폚. The product was discharged from the extruder as a beige solid suspended in an excess of liquid 2-methylimidazole. It solidified on cooling. The product was collected in one batch. The reagent was extruded only once. Several PXRD patterns of the extrudates as synthesized were examined, showing homogeneity in batches. All records were very similar to those of the simulated pattern of ZIF-8 obtained from the Cambridge Crystallographic Data Center (FAWCEN), although there were some differences between this and the simulated powder pattern for ZIF-8, This was caused by the excess of 2-methylimidazole contained in the pores of the resulting MOF.

Activation was performed by stirring 5 g of sample in 40 mL of HPLC grade methanol for 2 hours. This was filtered to give a white powder, which was again dipped in a solvent and stirred for an additional 2 hours. The suspension was filtered and the resulting solids were oven-dried at 150 &lt; 0 &gt; C for 2 hours. The PXRD of the activated product was very similar to the simulated PXRD record obtained for ZIF-8 (Figure 17).

Claims (26)

a. Providing a first reactant comprising at least one metal in ionic form;
b. Providing a second reactant comprising at least one organic ligand capable of associating with the metal in ionic form; And
c. Mixing said first and second reactants under long and sustained pressure and shear conditions sufficient to synthesize the metal-organic compound
Organic compound, wherein the metal-organic compound comprises at least one metal ion and at least one organic ligand, and wherein the organic ligand can be associated with the metal ion. The method of claim 1, wherein the pressure and shear are applied by an extrusion process. The method of claim 2, wherein the extrusion process is a screw-based extrusion process. The method of claim 3, wherein the screw-based process is a multiple screw-based extrusion process. 5. The method of claim 4, wherein the screw-based extrusion process is a biaxial extrusion process. The method of claim 5, wherein the biaxial extrusion process is a co-rotating biaxial extrusion process. 7. The method according to any one of claims 3 to 6, wherein the screw is partially or wholly intermeshing. 8. The process according to any one of claims 1 to 7, wherein the first reactant and / or the second reactant in steps (a) and (b) are dry reactants. 9. The process according to any one of claims 1 to 8, wherein the mixing of the reactants in step (c) is a straight-through mixing. 10. The process according to any one of claims 1 to 9, wherein the mixing of the reactants together in an extruder is carried out without the addition of a solvent. 8. The process according to any one of claims 1 to 7, which is carried out in the presence of a solvent. 12. The method of claim 11, wherein the solvent is any combination of hydrocarbons, alcohols, water, amides, amines, esters, ionic liquids, carboxylic acids, bases, ethers, halogenated solvents, aromatic solvents, sulfoxides or such solvents. 13. The process according to any one of claims 1 to 12, wherein the first reactant comprises an oxide and is in the form of a salt or salt. 14. The process of claim 13, wherein the first reactant is selected from the group consisting of metal nitrate, nitrite, oxide, hydroxide, alkoxide, aryloxide, carbonate, sulfate, acetate, formate, benzoate, acetylacetonate, fluoride, , Iodide, or a tartrate, a hydrogencarbonate, a phosphate, a hydrogen phosphate, a dihydrogen phosphate or a sulfonate. 15. The process according to claim 13 or 14, wherein the first reactant is a divalent first-period transition metal salt. 16. The process according to any one of claims 1 to 15, wherein the first and second reactants are exposed to further heat during step (c). 17. The method of claim 16, wherein the first and second reactants are exposed to a temperature within 20 [deg.] C of the melting point of one of the first and second reactants. 18. The process according to any one of claims 1 to 17, which is a continuous process. 19. The process according to any one of claims 2 to 18, wherein the first and second reactants are mixed prior to passing through the extruder. 20. The method according to any one of claims 1 to 19, further comprising the step (d) of heating the metal-organic compound formed in the subsequent heating step. 21. The method of claim 20, wherein the heating step involves a temperature change of up to 250 &lt; 0 &gt; C. 22. The process according to any one of claims 1 to 21, comprising two or more reactants to obtain a multi-metal and / or multi-crosslinked-material 2D or 3D metal-organic compound. 23. The method according to any one of claims 1 to 22, for the production of a metal-organic framework. 24. The method of claim 23, wherein the second reactant is an alkoxide, an aryl oxide, an imidazole, a carboxylate, a pyridine, an amine, a carboxylic acid, a diacid and / or a triacid moiety. 24. A multidimensional metal-organic compound formed at any time by a process as defined in any one of claims 1 to 24. 25. A metal-organic structure formed at any time by a process as defined in any one of claims 1 to 25.

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